Cell, cell stack device, module and module containing device

ABSTRACT

A cell may include a columnar support having a first main face and a second main face; and an element comprising a first electrode layer, a solid electrolyte layer, and a second electrode layer laminated in sequence on the first main face of the support. The porosity of at least one of the two end portions of the support in the longitudinal direction L may be lower than that of the central portion of the support in the longitudinal direction L.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/079,136 filed on Aug. 23, 2018, which is a national stage entryaccording to 35 U.S.C. 371 of PCT Application No. PCT/JP2017/005625filed on Feb. 16, 2017, which claims priority to Japanese ApplicationNo. 2016-034520 filed on Feb. 25, 2016, which are entirely incorporatedherein by reference.

TECHNICAL FIELD

The present disclosure relates to a cell, a cell stack assembly, amodule, and a module-accommodating assembly.

BACKGROUND

Various fuel cell systems including cell stack assemblies have beenproposed as next generation energy sources. Such a cell stack assemblyincludes fuel cells electrically connected in series and accommodated ina container.

The fuel cells in the cell stack assembly have lower end portions bondedto a manifold with a bonding agent, such as glass, and fuel gas that hasnot been consumed in power generation is combusted in upper end portionsof the fuel cells.

Unfortunately, such a cell stack assembly undergoes cracking in upperend portions and lower end portions of the fuel cells due toconcentration of stress on the upper and lower end portions, which mayimpair the long-term reliability. Thus, a proposed fuel cell is providedwith a reinforcement layer to enhance the robustness of the upper andlower end portions (see, for example, Patent Literature 1).

PL 1: WO2014/208730

SUMMARY

A cell according to the present disclosure may include: a columnarsupport having a first main face and a second main face; and an elementincluding a first electrode layer, a solid electrolyte layer, and asecond electrode layer, laminated in sequence on the first main face ofthe support. The porosity of at least one of two end portions of thesupport in the longitudinal direction is lower than that of the centralportion of the support in the longitudinal direction.

A cell stack assembly according to a non-limiting embodiment of thepresent disclosure includes a plurality of the cells described above,and one of the end portions of the support is bonded to a manifold witha bonding agent.

A module according to a non-limiting embodiment of the presentdisclosure accommodates the cell stack assembly described above.

A module accommodation assembly according to a non-limiting embodimentof the present disclosure includes an exterior case accommodating themodule described above and accessories for operation of the module.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 illustrates an exemplary hollow flat-plate cell according to anon-limiting embodiment: FIG. 1A is a side view of the cell at aninterconnection layer; and FIG. 1B is a side view of the cell at anoxygen electrode layer.

FIG. 2A is a cross-sectional view taken along lines A-A in FIGS. 1A and1B; FIG. 2B is a cross-sectional view taken along lines B-B in FIGS. 1Aand 1B.

FIG. 3 is a cross-sectional view taken along lines D-D in FIGS. 1A and1B.

FIG. 4 is an exemplary cell stack assembly according to a non-limitingembodiment: FIG. 4A is a schematic side view of the cell stack assembly;and FIG. 4B is an enlarged cross-sectional view of the cell stackassembly circled by dotted lines in FIG. 4A.

FIG. 5 is a side view seen from the interconnection layer andillustrating the cells of FIG. 1 fixed to a manifold.

FIG. 6 illustrates another exemplary cell according to a non-limitingembodiment: FIG. 6A is a side view at an interconnection layer of thecell; and FIG. 6B is a side view at an oxygen electrode layer of thecell.

FIG. 7A is a cross-section view taken along lines A-A in FIGS. 6A and6B; and FIG. 7B is a cross-sectional view taken along lines B-B in FIGS.6A and 6B.

FIG. 8 is a cross-sectional view taken along lines D-D in FIGS. 6A and6B.

FIG. 9 is an external perspective view of an exemplary fuel cell moduleaccording to a non-limiting embodiment.

FIG. 10 is a perspective view of a module-accommodating assemblyaccording to a non-limiting embodiment, where part of the assembly isnot illustrated.

DETAILED DESCRIPTION

A cell, a cell stack assembly, a module, and a module-accommodatingassembly will now be described in reference to FIGS. 1A to 10.

A solid oxide fuel cell (SOFC) will now be described as an exemplarycell. It should be noted that the same components are denoted by thesame reference numerals or symbols.

FIGS. 1A and 1B illustrate an exemplary cell according to a non-limitingembodiment. FIG. 1A is a side view of the cell at an interconnectionlayer. FIG. 1B is a side view of the cell at an oxygen electrode layer.FIG. 2A is a cross-sectional view taken along lines A-A in FIGS. 1A and1B. FIG. 2B is a cross-sectional view taken along lines B-B in FIGS. 1Aand 1B. FIG. 3 is a cross-sectional view taken along lines D-D in FIGS.1A and 1B.

In FIGS. 1A and 1B, a reference symbol C indicates the central portionof a support 2, a reference symbol E1 indicates the lower end portion ofthe support 2, and a reference symbol E2 indicates the upper end portionof the support 2.

A cell 1 in FIGS. 1A to 3 includes the conductive support 2 of a hollowflat-plate having a low-profile cross-section and a substantiallyelliptically cylindrical shape (in other words, an elliptically columnarshape). In the interior of the support 2, gas channels 2 a disposed atappropriate intervals extend in the longitudinal direction L of the cell1. The cell 1 is provided with various components on the support 2.

In the cell 1 illustrated in FIGS. 1A, 1B, and 2, the support 2 has twoopposite main faces n, i.e., a first main face and a second main face,and two opposite side faces m connecting the first main face to thesecond main face as is apparent from the shapes illustrated in FIGS. 2Aand 2B. A first electrode layer or porous fuel electrode layer 3 isprovided so as to cover the first main face n (bottom) and the two sidefaces m. Furthermore, a solid electrolyte layer 4 is provided so as tocover the fuel electrode layer 3. The solid electrolyte layer 4 iscomposed of a gas-impermeable ceramic. The ceramic may have a thicknessof 40 μm or less, alternatively 20 μm or less, or 15 μm or less inanother non-limiting embodiment to enhance the power generationcapacity.

In the cell 1 of FIGS. 1A to 3, a second electrode layer or oxygenelectrode layer 6 is provided on the solid electrolyte layer 4 adjacentto the first main face n. The solid electrolyte layer 4 is disposedbetween the oxygen electrode layer 6 and the fuel electrode layer 3.

The second main face (top) is provided with an interconnection layer 8composed of a gas-impermeable ceramic instead of the oxygen electrodelayer 6.

In other words, the cell 1 is provided with the fuel electrode layer 3and the solid electrolyte layer 4 extending from the first main face n(bottom) via the arcuate sides m to the second main face n (top). Theinterconnection layer 8 is laminated onto the solid electrolyte layer 4such that the interconnection layer 8 extends toward the left and rightends of the solid electrolyte layer 4.

The solid electrolyte layer 4 and the interconnection layer 8 are bothgas-impermeable and surround the support 2 such that fuel gascirculating inside does not leak to the outside environment. In otherwords, the solid electrolyte layer 4 and the interconnection layer 8define an elliptically cylindrical and gas-impermeable tube, whichserves as a fuel gas flow channel. Thus, fuel gas supplied to the fuelelectrode layer 3 and oxygen-containing gas supplied to the oxygenelectrode layer 6 are not permeated through the elliptically cylindricaltube.

Specifically, as illustrated in FIG. 1A, the interconnection layer 8having a rectangular planer shape extends toward the upper and lower endportions of the support 2 on the second main face n of the support 2. Asillustrated in FIG. 1B, the oxygen electrode layer 6 having arectangular and planar shape extends toward the upper and lower ends ofthe support 2 on the first main face n of the support 2.

The fuel electrode layer 3 and the oxygen electrode layer 6 separated bythe solid electrolyte layer 4 in the cell 1 together function as a powergeneration element. In detail, the oxygen-containing gas is fed to theexterior of the oxygen electrode layer 6 and the fuel gas(hydrogen-containing gas) is fed into the gas channels 2 a in thesupport 2. The gases are then heated to a predetermined operationaltemperature to generate power. Electric currents produced by such powergeneration is collected through the interconnection layer 8 on thesupport 2.

Components of the cell 1 according to a non-limiting embodiment will nowbe described.

The support 2 should be gas-permeable to allow the fuel gas to permeatethe fuel electrode layer 3 and should be conductive to collect powerthrough the interconnection layer 8. Thus the support may be composedof, for example, Ni and/or NiO and an inorganic oxide, such as a certainrare earth oxide.

The certain rare earth oxide is used to equalize the thermal expansioncoefficient of the support 2 to that of the solid electrolyte layer 4.The oxide of at least one rare earth element selected from the groupconsisting of Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm, and Pr, may be used incombination with Ni and/or NiO. Examples of the rare earth oxidesinclude Y₂O₃, Lu₂O₃, Yb₂O₃, Tm₂O₃, Er₂O₃, Ho₂O₃, Dy₂O₃, Gd₂O₃, Sm₂O₃,Pr₂O₃. Among these, Y₂O₃ and Yb₂O₃ are usable, which barely dissolve andreact with Ni and/or NiO, have a thermal expansion coefficientcomparable to that of the solid electrolyte layer 4, and are relativelyinexpensive.

In a non-limiting embodiment, in order to impart a sufficientconductivity and a thermal expansion coefficient equalized to that ofthe solid electrolyte layer 4 to the support 2, the volume ratio of theNi and/or NiO to a rare earth oxide may range from 35:65 to 65:35.

It should be noted that the support 2 may contain any other metalcomponent and oxide component within contents not impairing the requiredproperties.

The support 2 should have fuel gas permeability and is thus porous. Thesupport 2 may have an open porosity of 20% or more, in particular in therange of 25% to 50%. The support 2 may have an electroconductivity of300 S/cm or more, in particular 440 S/cm or more.

The length of the flat face n of the support 2 (the length of thesupport 2 in the width direction W) ranges, for example, from 15 mm to35 mm. The length of the arcuate side m (the length of the arc) rangesfrom 2 mm to 8 mm. The thickness of the support 2 (the distance betweenthe flat faces n) ranges from 1.5 mm to 5 mm. The height of the support2 ranges, for example, from 100 mm to 300 mm.

The fuel electrode layer 3 causes an electrode reaction and can becomposed of a known porous conductive ceramic. The fuel electrode layer3 may be composed of, for example, ZrO₂ or CeO₂ that contains dissolvedrare earth oxide in combination of Ni and/or NiO. The rare-earthelements listed above with respect to the support 2 can be used. Forexample, ZrO₂ (YSZ) containing dissolved Y₂O₃ can be combined with Niand/or NiO.

The content of ZrO₂ or CeO₂ containing dissolved rare earth oxide in thefuel electrode layer 3 may range from 35% to 65% by volume, and thecontent of Ni or NiO may range from 65% to 35% by volume. The openporosity of the fuel electrode layer 3 may be 15% or more, in particularin the range of 20% to 40%. The thickness of the fuel electrode layer 3may range from 1 μm to 30 μm.

The fuel electrode layer 3 should be disposed in parallel to the oxygenelectrode layer 6; hence, the fuel electrode layer 3 may be provided,for example, only on the flat face n at the bottom onto which the oxygenelectrode layer 6 is disposed. In other words, the fuel electrode layer3 may be provided only on the flat face n at the bottom of the support2, and the solid electrolyte layer 4 is provided on the flat face n onthe top and at the arcuate sides m of the support 2 where the fuelelectrode layer 3 is not disposed.

As described above, the solid electrolyte layer 4 may contain apartially or fully stabilized ZrO₂ containing dissolved rare earthoxide, such as Y, Sc, and Yb, in a molar content ranging from 3% to 15%as a main component. In a non-limiting embodiment, Y may be preferred asthe rare-earth element, as it is inexpensive. The material for the solidelectrolyte layer 4 should not be limited to the ceramics consisting ofpartially or fully stabilized ZrO₂, but may include known ceria-based orlanthanum-gallate-based metals containing dissolved rare earth elements,such as Gd and Sm.

The oxygen electrode layer 6 may be composed of a conductive ceramicconsisting of a so-called ABO₃ perovskite oxide. Such perovskite oxidesare composed of transition metals containing La, in particular, at leastone of LaMnO₃ based oxide, LaFeO₃ based oxide, and LaCoO₃ based oxide,all of which contain coexisting Sr and La in the A site, may be used ina non-limiting embodiment. LaCoO₃ based oxide may be preferred in anon-limiting embodiment because it has a high electroconductivity at anoperational temperature ranging from 600° C. to 1000° C. Theseperovskite oxides may contain Fe and Mn in addition to Co in the B site.

The oxygen electrode layer 6 should have gas permeability, for example,having an open porosity of 20% or more, or, alternatively, in the rangeof 30% to 50% in another non-limiting embodiment. The oxygen electrodelayer 6 may have a thickness in the range of 30 μm to 100 μm in view ofcollection of power.

The interconnection layer 8 is composed of a conductive ceramic. Theinterconnection layer 8 is exposed to the fuel gas (hydrogen-containinggas) and oxygen-containing gas and should thus have resistance toreduction and oxidation reactions. Thus, for example, lanthanum chromite(LaCrO₃) perovskite oxide is used as a conductive ceramic havingresistance to reduction and oxidation reactions. In order to equalizethe thermal expansion coefficient of the interconnection layer 8 to thatof the support 2 or the solid electrolyte layer 4, LaCrMgO₃ oxidecontaining Mg in the B site is used. The material for theinterconnection layer 8 may be any conductive ceramic.

The interconnection layer 8 may have a thickness in the range of 10 μmto 60 μm to prevent gas leakage and reduce its electric resistance. Thisrange of thickness can prevent gases from leaking and reduce theelectric resistance.

FIG. 4 illustrates an exemplary cell stack assembly 11 includingmultiple cells 1 electrically connected in series throughelectroconductive members 13. FIG. 4A is a schematic side view of thecell stack assembly 11; and FIG. 4B is an enlarged cross-sectional viewof the extracted portions of the cell stack assembly 11 circled bydotted lines in FIG. 4A. For clarity, the circled portions in FIG. 4Aare indicated by arrows in FIG. 4B.

In the cell stack assembly 11, the cells 1 are arrayed with theelectroconductive members 13 disposed between the cells 1 into a cellstack 12. The lower end portion E1 of each cell 1 is fixed to a manifold16 with an insulating bonding agent 17, such as glass seal. The manifold16 is configured to supply the cells 1 with fuel gas. Two elasticallydeformable electroconductive members 14 are fixed to the manifold 16like the lower end portions E1 of the cells 1, and tightly hold the cellstack 12 from its both sides in the direction of the array of cells 1.

The electroconductive members 14 of FIG. 4 are each provided with acurrent extractor 15 that extends along the array of cells 1 to theexterior and extracts the electric current generated in the cell stack12 (cells 1). As will be described below, the fuel gas discharged fromthe gas channel 2 a in the cell 1 is combusted by the reaction with theoxygen-containing gas in the upper end portion E2 of the cell 1. Thereaction can raise the temperature of the cell 1 to accelerate theactivation of the cell stack assembly 11.

FIG. 5 is a side view of the cell 1 shown in FIGS. 1A and 1B fixed tothe manifold, seen from the interconnection layer 8. In other words,FIG. 5 is a side view of the cell stack assembly 11 in FIG. 4 seen fromthe interconnection layer 8.

In FIG. 5, the lower end portion E1 of the cell 1 is bonded to themanifold 16 with the bonding agent 17. The interconnection layer 8containing lanthanum chromite is disposed in the central portion C inthe longitudinal direction L of the support 2.

In FIG. 3, the lower end portion E1 in the longitudinal direction L ofthe support 2 has lower porosity than the central portion C in thelongitudinal direction L of the support 2. The lower end portion E1 ofthe support 2 thereby has enhanced mechanical robustness againstcracking.

Although not illustrated in FIG. 3, the upper end portion E2 of thesupport 2 has lower porosity than the central portion C of the support2. The upper end portion E2 of the support 2 thereby has enhancedrobustness against cracking that will occur by combustive heat stress.

As illustrated in FIGS. 1A to 3, in the cell 1 according to anon-limiting embodiment, the second main face in the central portion Cof the support 2 is provided with the interconnection layer 8 containinglanthanum chromite. Thus, the second main face in the central portion Cof the support 2 may have a lower porosity than the first main face inthe central portion C. In other words, the second main face in thecentral portion C of the support 2 is provided with the interconnectionlayer 8 having a different shrinkage factor from the support 2.Meanwhile, the first main face of the support 2 is provided with thefuel electrode layer 3 and the solid electrolyte layer 4 each having ashrinkage factor comparable to that of the support 2. In the case thatthese are simultaneously baked, the second main face in the centralportion C of the support 2 is likely to undergo tensile stress; hence,the second main face in the central portion C of the support 2 has lowerporosity than the first main face in the central portion C, so that thesintered second main face of the support 2 is denser than the first mainface of the support 2. The second main face in the central portion C ofthe support 2 thereby has enhanced robustness, resulting in reductionsin tensile stress and cracking on the support 2.

The upper end portion and the lower end portion herein refer to two endportions of the support 2 equally divided in to seven portions in thelongitudinal direction L. The central portion C refers to the remainingdivided portion.

The first main face and the second main face herein refer to two sideportions of the support 2 equally divided into three portions in thewidth direction in the cross section in the longitudinal direction L ofthe support 2.

FIGS. 6A and 6B illustrate another exemplary cell 111 according to anon-limiting embodiment: FIG. 6A is a side view at the interconnectionlayer 8 of the cell 111; and FIG. 6B is a side view at the oxygenelectrode layer 6 of the cell 111. FIG. 7A is a cross-sectional viewtaken along lines A-A in FIGS. 6A and 6B; and FIG. 7B is across-sectional view taken along lines B-B in FIGS. 6A and 6B. FIG. 8 isa cross-sectional view taken along lines D-D in FIGS. 6A and 6B.

As illustrated in FIGS. 6A to 8, the cell 111 according to anon-limiting embodiment includes a support 2. The support 2 has a firstmain face and a second main face. At the lower end portion E1, thesupport 2 is provided with a solid electrolyte layer 4 and areinforcement layer 7 in sequence on the first main face and thereinforcement layer 7 on the second main face.

As described above, during a reduction reaction in the cell stack device11, an interconnection layer 8 is exposed to a reductive atmosphere andreductively expanded whereas the fixed lower end portion E1 of the cell111 may generate cracks due to stress on the lower end portion E1 of thesupport 2. Thus, as illustrated in FIGS. 6A to 8, the reinforcementlayer 7 is provided in the lower end portion E1 of the support 2. Thelower end portion E1 thereby has enhanced robustness, resulting in areduction in cracking.

In this case, as illustrated in FIG. 8, the second main face of thesupport 2 is provided with only the reinforcement layer 7 whereas thefirst main face of the support 2 is provided with two layers havingdifferent shrinkage factors (the solid electrolyte layer 4 and thereinforcement layer 7). Thus, the first main face of the support 2 ismore likely to undergo stress than the second main face and has a higherrisk of cracking than the second main face; hence, in the lower endportion E1 of the support 2, the first main face has a lower porositythan the second main face of the support 2. The first main face of thesupport 2 thereby has enhanced robustness, resulting in a reduction incracking.

The reinforcement layer 7 is composed of an oxide containing the samemain component as that of the solid electrolyte layer 4 and containing arare earth oxide in a different content from the solid electrolyte layer4.

In the case that the main component of the material of the solidelectrolyte layer 4 is, for example, ZrO₂ containing rare earth oxide,the reinforcement layer 7 may contain less rare earth oxide than thesolid electrolyte layer 4. In the case that the main component of thematerial of the solid electrolyte layer 4 is, for example, CeO₂containing rare earth oxide, the reinforcement layer 7 may contain morerare earth oxide than the solid electrolyte layer 4. The reinforcementlayer 7 thereby has enhanced robustness compared to the solidelectrolyte layer 4, to protect the lower end portion E1 readilyundergoing stress, resulting in a reduction in cracking on the support2. The main component herein refers to an element occupying 90% or moreby volume of the elements building up the solid electrolyte layer 4 andthe reinforcement layer 7.

In particular, in the case that the main component of the solidelectrolyte layer 4 is, for example, ZrO₂ containing dissolved Y₂O₃ in amolar content of 7% to 9%, power generation capacity can be enhanced.The main component of the reinforcement layer 7 may be ZrO₂ containingdissolved rare earth oxide, for example, Y₂O₃ in a molar content of 3%to 5% in a non-limiting embodiment.

Which of the solid electrolyte layer 4 or the reinforcement layer 7 hashigher robustness can be determined, for example, as follows: Anindenter is forced into exposed portions of the solid electrolyte layer4 or the reinforcement layer 7 under the same load in a fractured cell 1after mirror finishing. The robustness is determined from the maximumindentation depth with an ultra-microhardness tester.

The width of the reinforcement layer 7 (the width W of the cell 1) canbe appropriately determined and may be equal to or smaller than thewidth of the first main face n of the support 2. The length of thereinforcement layer 7 equals to that of the cell 1. Alternatively, thelength of the reinforcement layer 7 may be 3% to 10% of that of thesupport 2 in view of maintaining the effective area for power generationwhile enhancing robustness of the cell 1.

In view of enhanced robustness, the thickness of the reinforcement layer7 may be increased compared to that of the solid electrolyte layer 4.Thus, the thickness of the reinforcement layer 7 may range, for example,30 μm to 100 μm whereas the thickness of the solid electrolyte layer 4may be thinner than 30 μm.

An exemplary method for manufacturing the cell 1 according to anon-limiting embodiment will now be described.

For example, powdered Ni and/or NiO, powdered rare earth oxide, such asY₂O₃, an organic binder, and a solvent are mixed to prepare a clay soil.A green compact of a support is prepared by extrusion molding with theclay soil, and is then dried. The green compact of the support may becalcined for 2 to 6 hours at a temperature in the range of 900° C. to1000° C.

Subsequently, raw materials of NiO and ZrO₂ (YSZ) containing dissolvedY₂O₃ are weighed and mixed in accordance with a predeterminedproportion. The powder mixture is then blended with an organic binderand solvent into a slurry for fuel electrode.

The powdered ZrO₂ containing dissolved rare earth oxide are then mixedwith toluene, a powdered binder (containing higher molecules thanpowdered binder adhering to powdered ZrO₂ as described below, such asacrylic resin), and a commercially available dispersant into slurry. Theslurry is then shaped into a sheeted solid electrolyte layer compactthrough, for example, doctor blading.

The slurry for fuel electrode is applied to the resulting sheeted solidelectrolyte layer compact and dried into a fuel electrode compact. Asheeted laminated compact is eventually produced. The sheeted laminatedcompact of the fuel electrode compact and solid electrolyte layercompact is laminated on the green compact of the support such that theface of the fuel electrode compact comes into contact with the greencompact of the support.

Subsequently, the laminated compact is calcined for 2 to 6 hours at atemperature in the range of 800° C. to 1200° C. to yield a calcinedcompact.

For example, powdered Ni and/or NiO having a smaller particle size thanthe base powder of the support compact is then mixed with rare earthoxide powder, such as Y₂O₃ having a particle size equal to or smallerthan the base powder of the support compact, an organic binder, and asolvent to yield a slurry to be sintered. Instead, a sintering agent,such as boron oxide, ferric oxide, and a lanthanum chromite-basedperovskite oxide (LaCrO₃ based oxide) may be mixed with a binder and asolvent to prepare a slurry to be sintered.

The slurry is applied to a targeted site of the calcined compact or thecalcined compact is coated with or immersed in the slurry, and thecompact is recalcined for 2 to 6 hours at a temperature in the range of800° C. to 1200° C.

The production of the cell 1 including the reinforcement layer 7illustrated in FIGS. 6A and 6B employs, for example, a slurry of thepowdered ZrO₂ containing less dissolved rare earth oxide than the slurryfor the solid electrolyte layer compact described above and a powderedbinder. Such a slurry is applied to the solid electrolyte layer compact(calcined compact) in the lower end portion E1 of the support 2 and isdried.

Base powder for the interconnection layer (such as powdered LaCrMgO₃based oxide) is mixed with an organic binder and a solvent to prepare aslurry for the interconnection layer. Subsequently, the slurry isapplied to the solid electrolyte compact (calcined compact) such thatthe interconnection layer compact is laminated on the solid electrolytecompact at its ends. In the case of production of the cell 1 having thereinforcement layer 7 in FIGS. 6A and 6B, the slurry is applied suchthat the interconnection layer compact is laminated on the compact ofthe reinforcement layer 7 at its ends.

The laminated compact is subjected to debinding and simultaneoussintering (simultaneous baking) for 2 to 6 hours at a temperature in therange of 1400° C. to 1450° C. in an oxygen-containing atmosphere.

The slurry containing base powder for the oxygen electrode layer (suchas powdered LaCoO₃ based oxide), a solvent, and a pore forming agent isapplied to the solid electrolyte layer by, for example, dipping and isbaked for 2 to 6 hour at a temperature in the range of 1000° C. to 1300°C. The cell 1 having the structure according to a non-limitingembodiment in FIGS. 1A and 1B or FIGS. 6A and 6B can be therebymanufactured.

FIG. 9 is an external perspective view of an exemplary fuel cell module18 accommodating the cell stack assembly 11 in a container. The fuelcell module 18 accommodates the cell stack assembly 11 illustrated inFIG. 4 in a cuboidal container 19.

In order to feed fuel gas into the cells 1, a reformer 20 reforming araw fuel, such as natural gas and heating oil, is disposed over the cellstack 12. The fuel gas generated in the reformer 20 is fed to themanifold 16 through a gas flow tube 21 and fed into the gas channels 2 adisposed in the cell 1 through the manifold 16.

In FIG. 9, part of the container 19 is detached (in the direction fromthe rear to the front), and the cell stack assembly 11 and the reformer20 are drawn backward from the container 19. In the module 18 of FIG. 9,the cell stack assembly 11 can be slid into the container 19. The cellstack assembly 11 may include the reformer 20.

An oxygen-containing gas introducing member 22 in the container 19 isdisposed between the opposing cell stacks 12 on the manifold 16 in FIG.9. The oxygen-containing gas is fed to the lower end portion of the cell1 so as to flow from the lower end portion to the upper end portion atboth sides of the cell 1 in accordance with the flow of the fuel gas.The fuel gas discharged from the gas channels 2 a in the cell 1 reactswith the oxygen-containing gas to be combusted in the upper end portionof the cell 1, resulting in an increase in temperature of cell 1 andacceleration of the activation of the cell stack assembly 11. Thecombustion of the fuel gas by oxygen-containing gas discharged from therespective gas channels 2 a in the cells 1 in the upper end portions ofthe cells 1 allows the reformer 20 over the cells 1 (cell stacks 12) tobe warmed. Thus, the reformer 20 can effectively promote the reformingreaction.

In the module 18 according to a non-limiting embodiment, the cell stackassembly 11 including the cells 1 is accommodated in the container 19.Thus the module 18 has an enhanced long-term reliability.

FIG. 10 is a perspective view of an exemplary fuel cell assembly or amodule-accommodating assembly accommodating the module 18 of FIG. 9 andaccessories operating the cell stack assembly 11 in an exterior case. InFIG. 10, part of the configuration is not illustrated.

A module-accommodating assembly 23 in FIG. 10 includes an exterior caseincluding pillars 24 and outer plates 25 and divided in upper and lowerspaces by a partition panel 26. The upper space is referred to as amodule chamber 27 accommodating the module 18 described above, and thelower space is referred to as an accessary chamber 28 accommodatingaccessories for operation of the module 18. The accessories accommodatedin the accessary chamber 28 are not illustrated.

The partition panel 26 is provided with a ventilation hole 29circulating air in the accessary chamber 28 to the module chamber 27.One of the outer plates 25 of the module chamber 27 is provided with anair vent 30 for discharge of air from the module chamber 27.

The module-accommodating assembly 23 accommodates the above module 18having enhanced long-term reliability in the module chamber 27. Thus,the long-term reliability of the module-accommodating assembly 23 isalso enhanced.

In the above non-limiting embodiment, a fuel cell, a cell stackassembly, a fuel cell module, and a fuel cell assembly have beendescribed. The present disclosure, however, should not be limited to anyone embodiment described above. The disclosure is applicable to a solidoxide electrolysis cell (SOEC) that is supplied with vapor and voltageto electrolyze the vapor (water) into hydrogen and oxygen (O₂). In thiscase, both ends of the cell are fixed to the manifold with a bondingagent in a cell stack assembly. Thus, the upper and lower end portionseach have a lower porosity than the central portion such that thesupport has enhanced robustness at the ends, resulting in a reduction incracking, and thus the cell has enhanced long-term reliability. Thedisclosure is also applicable to a cell stack assembly including thiscell, a module, and a module-accommodating assembly, which have enhancedlong-term reliability.

EXAMPLES

Powdered NiO having an average particle size of 0.5 μm was mixed withpowdered Y₂O₃ having an average particle size of 2.0 μm, an organicbinder, and a solvent to prepare a clay soil. A green compact of asupport was prepared by extrusion molding with the clay soil and wasthen dried and degrease. A conductive green compact of the support wasthus produced. NiO and Y₂O₃ contents in the green compact of the supportwere 48% and 52%, respectively, by volume after the reduction reaction.

Powdered ZrO₂ containing dissolved 8 mol % Y₂O₃ and having a particlesize of 0.8 μm, which was measured by the Microtrac scheme, was mixedwith a powdered binder and a solvent. The resulting slurry was shapedinto a solid electrolyte layer sheet by doctor blading.

Powdered NiO having an average particle size of 0.5 μm was mixed withpowdered ZrO₂ containing dissolved Y₂O₃, an organic binder and a solventto prepare a slurry for a fuel electrode layer. The slurry was appliedto the solid electrolyte layer sheet by screen printing and then driedto yield a fuel electrode layer compact.

The solid electrolyte layer sheet was laminated on the sheeted fuelelectrode layer compact. This sheeted compact was laminated on the greencompact of the support at a predetermined position such that the face ofthe fuel electrode layer compact came into contact with the greencompact of the support.

Then, the laminated compact was calcined for 3 hours at 1000° C. toyield a calcined compact.

Subsequently, powdered NiO having an average particle size of 0.05 μmwas mixed with powdered Y₂O₃ having an average particle size of 0.2 μm,an organic binder, and a solvent to prepare a slurry to be sintered. Atargeted site of the calcined compact was coated with or immersed in theslurry, and the compact was recalcined for 3 hours at 1000° C. In a cellof Example in Table 1 to be described below, the lower end portion ofthe compact was immersed in the slurry. In another cell of Example inTable 2, the slurry was applied to only the first main face (adjacent tothe fuel electrode layer) in the lower end portion of the green compactof the support. In another cell of Example in Table 3, the slurry wasapplied to only a second main face (adjacent to an interconnectionlayer) in the central portion of the green compact of the support.

In Example and Comparative Example in Table 2, a slurry was applied to afirst main face in the lower end portion of the green compact of thesupport to yield a reinforcement layer compact, where the slurry was amixture of powdered ZrO₂ containing dissolved 3 mol % Y₂O₃ and having aparticle size of 0.8 μm, which was measured by the Microtrac scheme, apowdered binder, and a solvent.

Subsequently, La(Mg_(0.3)Cr_(0.7))_(0.96)O₃ having an average particlesize of 0.7 μm was mixed with an organic binder and a solvent to preparea slurry for the interconnection layer. The prepared slurry was appliedto an exposed site, which was not covered by the fuel electrode layer(and the solid electrolyte layer), of the support, in the centralportion of the calcined solid electrolyte layer compact extending towardthe upper and lower end portions.

The laminated compact was subject to debinding and simultaneous burningfor 2 hours at 1450° C. in the atmosphere, and then the slurry for theoxygen electrode layer was applied to the solid electrolyte layercompact. The laminated compact was then baked for 2 to 6 hours at 1000°C. to 1300° C. The cell was thereby produced.

The produced cell had dimensions of 25 mm by 170 mm. The support 2 had athickness of 2 mm (the distance between the flat faces n). The fuelelectrode layer had a thickness of 10 μm. The solid electrolyte layerhad a thickness of 10 μm. The interconnection layer had a thickness of50 μm.

In Comparative Example, components were prepared as in Example exceptthat the compact was not coated with or immersed in the slurry.

Seven cells according to Example were prepared and arrayed betweenelectroconductive members and fixed to a manifold with a bonding agentto build a cell stack assembly. Similarly, seven cells according toComparative Example were prepared and arrayed into a cell stackassembly. The cell stack assembly was subjected to a reduction reaction.An endurance test, for example, a heat cycle test was then conducted andthe occurrence of cracking on the supports of the cells was observed,for example, visually or metallographically.

The porosity was determined as follows: three of the seven cellsaccording to the Example and the Comparative Example were arbitrarilytaken from the cell stack assembly, and then cut and used formeasurement of the porosity by Archimedes' method. The cut samples eachhad dimensions of 20 mm by 10 mm and a thickness of 1 mm. The threesamples were taken from each area. Each porosity was the average of thethree samples. The results are indicated below.

Table 1 shows the porosities at the central portion and the lower endportion of the support and occurrence of cracking on the support.

Table 2 shows the porosities at the first main face and the second mainface of the lower end portion of the support and occurrence of crackingon the support.

Table 3 shows the porosities of the first main face and the second mainface in the central portion of the support and occurrence of cracking onthe support.

In the column of occurrence of cracking on the support in Tables 1 to 3,a sample with no crack on the support is indicated as “not found”, and asample with at least a crack on the support is indicated as “found”.

TABLE 1 POROSITY (%) CRACKING CENTRAL LOWER ON PORTION END PORTIONSUPPORT EXAMPLE 32.0 29.1 NOT FOUND COMPARATIVE 32.0 32.0 FOUND EXAMPLE

TABLE 2 POROSITY (%) FIRST MAIN SECOND MAIN FACE IN FACE IN CRACK- LOWEREND LOWER END ING PORTION OF PORTION ON SUPPORT OF SUPPORT SUPPORTEXAMPLE 29.1 30.4 NOT FOUND COMPARA- 32.0 32.0 FOUND TIVE EXAMPLE

TABLE 3 POROSITY (%) FIRST MAIN FACE SECOND MAIN CRACK- IN CENTRAL FACEIN CENTRAL ING PORTION OF PORTION OF ON SUPPORT SUPPORT SUPPORT EXAMPLE32.0 29.4 NOT FOUND COMPARA- 32.0 32.0 FOUND TIVE EXAMPLE

As apparent from the results on Table 1, Comparative Example has thesame porosity at the lower end portion and the central portion of thesupport and has cracking on the support. In contrast, Example has alower porosity at the lower end portion of the support than at thecentral portion and has no cracking.

As apparent from the results on Table 2, the Comparative Example has thesame porosity at the first main face and the second main face of thesupport and has cracking on the support. In contrast, Example has alower porosity at the first main face of the support than at the secondmain face and has no cracking.

As apparent from the results on Table 3, Comparative Example has thesame porosity at the first main face and the second main face in thecentral portion of the support and has cracking on the support. Incontrast, Example has a lower porosity at the second main face in thecentral portion of the support than at the first main face in thecentral portion and has no cracking.

REFERENCE SIGNS LIST

-   1 cell-   2 support-   2 a gas channel-   3 first electrode layer (fuel electrode layer)-   4 solid electrolyte layer-   6 second electrode layer (oxygen electrode layer)-   7 reinforcement layer-   8 interconnection layer-   11 cell stack assembly-   18 module (fuel cell module)-   23 module-accommodating assembly (fuel cell assembly)

What is claimed is:
 1. A cell comprising: an electrically conductive columnar support; and an element comprising a first electrode layer, a solid electrolyte layer, and a second electrode layer laminated in sequence on the electrically conductive columnar support, wherein both end portions of the electrically conductive columnar support in the longitudinal direction have lower porosity than that of a central portion of the electrically conductive columnar support in the longitudinal direction.
 2. The cell according to claim 1, further comprising: a reinforcement layer laminated on the solid electrolyte layer at one of the end portions of the electrically conductive columnar support, the reinforcement layer comprising an oxide that further comprises a rare earth oxide, wherein the solid electrolyte layer comprises the oxide and also further comprises the rare earth oxide in a different content than the rare earth oxide in the reinforcement layer.
 3. The cell according to claim 1, further comprising: an interconnector, wherein the electrically conductive columnar support comprises a first outer face and a second outer face, the element is disposed on the first outer face, the interconnector is disposed on the second outer face, and a central portion of the electrically conductive columnar support at the first outer face has a higher porosity than the second outer face.
 4. The cell according to claim 1, wherein the electrically conductive columnar support comprises a first outer face and a second outer face, and a lower end portion of the end portions at the first outer face has a lower porosity than the second outer face.
 5. A cell stack assembly comprising a plurality of the cells according to claim 1, wherein one or both of the end portions of the electrically conductive columnar support of cells of the plurality of cells is bonded to a manifold with a bonding agent.
 6. A module accommodating the cell stack assembly according to claim 5 in a container.
 7. A module-accommodating assembly comprising an exterior case accommodating the module according to claim 6 and accessories configured to operate the module.
 8. A cell comprising: a columnar support comprising: in a longitudinal direction, a lower end portion, an upper end portion, and a central portion between the lower end portion and the upper end portion; and an element comprising a first electrode layer, a solid electrolyte layer, and a second electrode layer laminated in sequence on the columnar support, wherein an entirety of the columnar support has a porosity of 20% or more, and the upper end portion has a lower porosity than that of the central portion.
 9. The cell according to claim 8, further comprising: an interconnector, wherein the columnar support further comprises a first outer face and a second outer face, the element is disposed on the first outer face, the interconnector is disposed on the second outer face, and in the central portion the first outer face has a higher porosity than the second outer face.
 10. The cell according to claim 8, wherein the columnar support comprises a first outer face and a second outer face, and in the lower end portion the first outer face has a lower porosity than the second outer face.
 11. The cell according to claim 8, further comprising: a reinforcement layer laminated on the solid electrolyte layer at the lower end portion, the reinforcement layer comprising an oxide that further comprises a rare earth oxide, wherein the solid electrolyte layer comprises the oxide and also further comprises the rare earth oxide in a different content than the rare earth oxide in the reinforcement layer.
 12. A cell stack assembly comprising a plurality of the cells according to claim 8, wherein the lower end portion of cells of the plurality of the cells is bonded to a manifold with a bonding agent.
 13. A module accommodating the cell stack assembly according to claim 12 in a container.
 14. A module-accommodating assembly comprising an exterior case accommodating the module according to claim 13 and accessories configured to operate the module. 